EP0365974A2 - Procédé de préparation d'un copolymère éthylène-propylène - Google Patents

Procédé de préparation d'un copolymère éthylène-propylène Download PDF

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Publication number
EP0365974A2
EP0365974A2 EP89119234A EP89119234A EP0365974A2 EP 0365974 A2 EP0365974 A2 EP 0365974A2 EP 89119234 A EP89119234 A EP 89119234A EP 89119234 A EP89119234 A EP 89119234A EP 0365974 A2 EP0365974 A2 EP 0365974A2
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EP
European Patent Office
Prior art keywords
group
propylene
ethylene
radicals
metallocene
Prior art date
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Granted
Application number
EP89119234A
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German (de)
English (en)
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EP0365974B1 (fr
EP0365974A3 (fr
Inventor
Martin Dr. Antberg
Walter Dr. Spaleck
Jürgen Dr. Rohrmann
Hartmut Dr. Lüker
Andreas Dr. Winter
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Hoechst AG
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Hoechst AG
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Priority to AT89119234T priority Critical patent/ATE99338T1/de
Publication of EP0365974A2 publication Critical patent/EP0365974A2/fr
Publication of EP0365974A3 publication Critical patent/EP0365974A3/fr
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Publication of EP0365974B1 publication Critical patent/EP0365974B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/902—Monomer polymerized in bulk in presence of transition metal containing catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/909—Polymerization characterized by particle size of product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to a process for the preparation of predominantly crystalline ethylene-propylene copolymers of various molecular weight ranges with the aid of metallocene-aluminoxane catalysts.
  • metallocene-aluminoxane catalyst systems in liquid propylene as a dispersant and monomer has also been proposed (cf. DE 3726 067). With these metallocenes and under the conditions used, however, highly isotactic polypropylene is obtained as a polymerization product. A preactivation method for the metallocenes is also proposed, which leads to an increase in the activity of the catalysts and to an improvement in the grain morphology of the polymers.
  • the invention thus relates to a process for producing an ethylene-propylene copolymer with a propylene unit content of less than 15 mol%, based on the total polymer, by polymerizing ethylene and propylene in a suspension medium at a temperature of -60 to 90 ° C, at a pressure of 0.5 to 150 bar, in the presence of a catalyst which consists of a metallocene and an aluminoxane of the formula IV for the linear type and / or formula V for the cyclic type, where in the formulas IV and V R20 is a C1-C6 alkyl group and q is an integer from 2 to 50, characterized in that the polymerization is carried out in liquid propylene as a suspending agent, the ratio of the partial pressure P C2 of the ethylene in the gas phase to the partial pressure P C3 of the propylene in the gas phase is and the metallocene is a compound of the formulas I, II or III where in formulas I, II and III M1 is
  • the catalyst to be used for the process according to the invention consists of a metallocene compound of structure types A, B or C according to the formulas I, II or III and an aluminoxane.
  • M1 is a metal from group IVb, Vb or VIb of the periodic table, for example titanium, zircon, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably zircon and hafnium.
  • R1 and R2 are the same or different and represent a hydrogen atom, a halogen atom, preferably chlorine, a C1-C10, preferably C1-C3 alkyl group, a C1-C10, preferably C1-C3 alkoxy group, a C6-C10-, preferably C6-C8 aryl group, a C6-C10, preferably C6-C8 aryloxy group, a C2-C10, preferably C2-C4 alkenyl group, a C7-C40, preferably C7-C10 arylalkyl group, a C7-C40 -, preferably C7-C12-alkylaryl group, a C8-C40-, preferably C8-C12-arylalkenyl group.
  • a halogen atom preferably chlorine
  • a C1-C10, preferably C1-C3 alkyl group a C1-C10, preferably C1-C3 alkoxy
  • R3 and R4 are the same and different, preferably the same, and mean an indenyl or tetrahydroindenyl radical, the five-membered rings of the radicals R3 and R4 forming a sandwich structure with the central atom M1.
  • R5 and R6 are the same or different, preferably the same, and are substituents in the 3-position of the five-membered rings mentioned, which may have the following structure: where M2 is silicon, germanium or tin, preferably silicon.
  • R8, R9 and R10 are the same or different, preferably the same, and mean a halogen atom, a C1-C10 alkyl group, preferably C1-C4 alkyl group, in particular methyl group, a C1-C10 fluoroalkyl group, preferably CF3 group, a C6- C10-, preferably C6-C8-aryl group, a C6-C10-fluoroaryl group, preferably pentafluorophenyl group, a C1-C10-, preferably C1-C4-alkoxy group, especially methoxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C
  • R11, R12, R13 and R14 are the same or different and represent a hydrogen atom, a halogen atom, a C1-C10 alkyl group, preferably C1-C4 alkyl group, especially methyl group, a C1-C10 fluoroalkyl group, preferably CF3 group, a C6 -C10-, preferably C6-C8-aryl group, a C6-C10-fluoroaryl group, preferably pentafluorophenyl group, a C1-C10-, preferably C1-C4-alkoxy group, especially methoxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-arylalkyl group, a C8-C40-, preferably C8-C12-arylalkenyl group or a C7-C40-, preferably C7-C12-alkylaryl group.
  • R7 forms a ring with the residues R3 and R4, the linking of R7 with the residues R3 and R4 in the 1-position of the radicals R3 and R4 takes place.
  • R3 and R4 are indenyl radicals, they can be converted into tetrahydroindenyl radical by hydrogenation of the compound (I) by known methods.
  • a particularly preferred metallocene of structure type A is ethylene bis [1- (3-trimethylsilylindenyl)] zirconium dichloride.
  • R15 is where M2, R11, R12, R13 and R14 have the abovementioned meaning and R16 and R17 have the meaning of R11, R12, R13 or R14.
  • n 3, 4 or 5 and p is 1, 2 or 3.
  • R15 forms a ring with the radicals R3 and R4, the linking of R15 with R3 and R4 in the 1-position of the radicals R3 and R4.
  • R3 and R4 are indenyl radicals, they can be converted into tetrahydroindenyl radicals by hydrogenating the compound (II) by known methods.
  • a particularly preferred metallocene of structure type B is propylene bis (1-indenyl) zirconium dichloride.
  • Cp represents a cyclopentadienyl radical
  • n means the numbers 3, 4 or 5.
  • R18 and R19 are identical or different, preferably identical radicals on the cyclopentadienyl rings and mean a halogen atom, a C1-C10 alkyl group, preferably C1-C4 alkyl group, in particular methyl group, a C1-C10 fluoroalkyl group, preferably CF3 group, a C6 -C10-, preferably C6-C8-aryl group, a C6-C10-fluoroaryl group, preferably pentafluorophenyl group, a C1-C10-, preferably C1-C4-alkoxy group, especially methoxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-arylalkyl group, a C8-C40-, preferably C8-C12-arylalkenyl group or a C7-C40-, preferably C7-C12-
  • a particularly preferred metallocene of structure type C is bis (pentamethylcyclopentadienyl) zirconium dichloride.
  • the catalyst system to be used according to the invention also contains an aluminum alkyl compound as an activator.
  • This activator is an aluminoxane of the formula IV for the linear type and / or formula V for the cyclic type.
  • R20 is a C1-C6 alkyl group, preferably methyl, ethyl or isobutyl, in particular methyl, and q is an integer from 2 to 50, preferably 10 to 40.
  • the exact structure of the aluminoxane is not certain.
  • the aluminoxane can be made in a number of ways.
  • finely powdered copper sulfate pentahydrate is slurried in toluene and so much aluminum trialkyl is added in a glass flask under inert gas at about -20 ° C that about 1 mol of CuSO4 ⁇ 5H2O is available for every 4 Al atoms.
  • the reaction mixture is left for 24 to 48 hours at room temperature, cooling being necessary if necessary so that the temperature does not rise above 30 ° C.
  • the aluminoxane dissolved in the toluene is then filtered off from the copper sulfate and the solution is concentrated in vacuo. It is believed that in this manufacturing process, the low molecular weight aluminoxanes condense to higher oligomers with elimination of aluminum trialkyl.
  • aluminoxanes are obtained if aluminum trialkyl, preferably aluminum trimethyl, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted with aluminum salts, preferably aluminum sulfate, containing water of crystallization at a temperature of -20 to 100.degree.
  • the volume ratio between solvent and the aluminum alkyl used is 1: 1 to 50: 1 - preferably 5: 1 - and the reaction time, which can be controlled by splitting off the alkane, is 1 to 200 hours - preferably 10 to 40 hours.
  • Aluminum salts containing water of crystallization those with a high content of are used in particular Have crystal water.
  • Aluminum sulfate hydrate is particularly preferred, especially the compounds Al2 (SO4) 3 ⁇ 16H2O and Al2 (SO4) 3 ⁇ 18H2O with the particularly high crystal water content of 16 or 18 mol H2O / mol Al2 (SO4) 3.
  • a further variant for the preparation of aluminoxanes consists in dissolving aluminum trialkyl, preferably aluminum trimethyl, in the suspension medium, preferably in the liquid monomer, in heptane or toluene, which is present in the polymerization vessel, and then reacting the aluminum compound with water.
  • the transition metal compound is preactivated in solution.
  • the metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon.
  • An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon.
  • Toluene is preferably used.
  • the concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total solution.
  • the metallocene can be used in the same concentration, but it is preferably used in an amount of 10-1 mol per mol of aluminoxane.
  • the preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. One works at a temperature of -78 ° C to 100 ° C, preferably 0 to 70 ° C.
  • the catalyst system to be used according to the invention is used for the copolymerization of ethylene with propylene and optionally a further 1-olefin with 4 to 18 C atoms, e.g. Butene- (1), hexene- (1), 4-methylpentene- (1), octene- (1) are used.
  • the polymerization is carried out in liquid propylene continuously or batchwise, in one or more stages at a temperature of -60 ° C. to 90 ° C., preferably 20 ° C. to 70 ° C.
  • the total pressure is 0.5 to 150, preferably 14.5 to 120 bar.
  • the metallocene compound is used in a concentration, based on the transition metal, of 10 ⁇ 3 to 10 ⁇ 8, preferably 10 ⁇ 4 to 10 ⁇ 7 mol of transition metal per dm3 of liquid propylene.
  • the aluminoxane is used in a concentration of 10 ⁇ 4 to 10 ⁇ 1 mol, preferably 10 ⁇ 3 to 10 ⁇ 2 mol per dm3 of liquid propylene. In principle, however, higher concentrations are also possible.
  • the molecular weight of the polymer can be regulated in a known manner; hydrogen is preferably used for this purpose.
  • the process according to the invention increases the versatility of using plants in which polymerisation can take place in liquid propylene.
  • the predominantly crystalline ethylene-propylene copolymers are called "HDPE"("High Density Poly-Ethylene"), “MDPE”("Medium Density Poly-Ethylene”) and “LLDPE " ("Linear Low Density Poly-Ethylene”) obtained.
  • HDPE High Density Poly-Ethylene
  • MDPE Medium Density Poly-Ethylene
  • LLDPE Linear Low Density Poly-Ethylene
  • Mean it VZ viscosity number in cm3 / g
  • M w molar mass weight average in g / mol
  • M w / M n molecular weight distribution determined by gel permeation chromatography (GPC)
  • the propylene contents of the polymers were determined by 13 C-NMR spectroscopy, the crystallinities as relative crystallinities by IR spectroscopy.
  • the melt index MFI 190 / 2.16 has been determined according to DIN 53735, the density according to DIN 53479, method A.
  • the melting points were determined by DSC measurements.
  • the ethylene bis [1- (3-trimethylsilylindenyl)] zirconium dichloride was used as the metallocene.
  • This compound can exist as a chiral isomer (in the form of a racemic mixture of two optically active enantiomers) or as a non-chiral meso isomer.
  • the preparation used had a ratio of racemate to meso form such as 3.5: 1.
  • the product was obtained in the form of a coarse-grained powder which had a bulk density of 0.35 g / cm 3 and the following particle size distribution, determined by sieving: Grain size proportion of total ( ⁇ m) (% By weight) (% By weight) ⁇ 100 2.1 2.1 100-200 7.5 9.6 200-300 17.5 27.1 300-400 14.8 41.9 400-500 11.4 53.3 500 - 630 13.2 66.5 630-800 12.4 78.9 800 - 1000 11.4 90.3 > 1000 9.7 100.0
  • a dry 70 dm3 kettle was first flushed with nitrogen, then with ethylene and then filled with 40 dm3 of liquid propylene.
  • the temperature was then raised to 51 ° C., which resulted in a pressure of 20.1 bar above the liquid in the gas phase.
  • a total pressure of 22.1 bar was set by adding hydrogen and then a total pressure of 50 bar by adding ethylene.
  • the partial pressure ratio P C2 / P C3 was 1.39.
  • the product had no uniform melting point, the DSC curve showed peaks at 88 ° C, 101 ° C and 114 ° C.
  • a dry 70 dm3 kettle was first flushed with nitrogen, then with ethylene and then filled with 40 dm3 of liquid propylene.
  • the temperature was then raised to 65 ° C., which resulted in a pressure of 26.8 bar above the liquid in the gas phase.
  • a total pressure of 28.3 bar was then set by adding hydrogen and then a total pressure of 46 bar by adding ethylene.
  • the partial pressure ratio P C2 / P C3 was thus 0.66.
  • propylene bis (1-indenyl) zirconium dichloride was used as the metallocene.
  • a dry 15 dm3 kettle was first flushed with nitrogen, then with ethylene and then filled with 10 dm3 of liquid propylene.
  • the pressure in the gas phase above the liquid reached 12.2 bar.
  • a total pressure of 33 bar was then set by adding ethylene, and the partial pressure ratio P C2 / P C3 was 1.7.
  • 1,1,4,4-tetramethyl-1,4-disilabutylenebis (1'-indenyl) zirconium dichloride was used as the metallocene. 95% of the compound was in the form of the racemic mixture of the chiral enantiomers.
  • bis (pentamethylcyclopentadienyl) zirconium dichloride was used as the metallocene.
  • a dry 70 dm3 kettle was first flushed with nitrogen, then with ethylene and then filled with 40 dm3 of liquid propylene.
  • the temperature was then raised to 45 ° C., which resulted in a pressure of 17.6 bar above the liquid in the gas phase.
  • a total pressure of 50 bar was set by adding ethylene.
  • the partial pressure ratio P C2 / P C3 was 1.84.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP89119234A 1988-10-22 1989-10-17 Procédé de préparation d'un copolymère éthylène-propylène Expired - Lifetime EP0365974B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89119234T ATE99338T1 (de) 1988-10-22 1989-10-17 Verfahren zur herstellung eines ethylen-propylen- copolymers.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3836059A DE3836059A1 (de) 1988-10-22 1988-10-22 Verfahren zur herstellung eines ethylen-propylen-copolymers
DE3836059 1988-10-22

Publications (3)

Publication Number Publication Date
EP0365974A2 true EP0365974A2 (fr) 1990-05-02
EP0365974A3 EP0365974A3 (fr) 1992-01-15
EP0365974B1 EP0365974B1 (fr) 1993-12-29

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EP89119234A Expired - Lifetime EP0365974B1 (fr) 1988-10-22 1989-10-17 Procédé de préparation d'un copolymère éthylène-propylène

Country Status (9)

Country Link
US (1) US5086134A (fr)
EP (1) EP0365974B1 (fr)
JP (1) JP2929544B2 (fr)
AT (1) ATE99338T1 (fr)
AU (1) AU615113B2 (fr)
CA (1) CA1338333C (fr)
DE (2) DE3836059A1 (fr)
ES (1) ES2061877T3 (fr)
ZA (1) ZA897954B (fr)

Cited By (3)

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WO1996013529A1 (fr) * 1994-10-31 1996-05-09 Dsm N.V. Composition catalytique et procede de polymerisation d'une olefine
EP0743324A2 (fr) * 1995-05-16 1996-11-20 Union Carbide Chemicals & Plastics Technology Corporation Production de polyéthylène utilisant des métallocènes stéréoisomériques
WO2003008465A2 (fr) * 2001-07-19 2003-01-30 Univation Technologies, Llc Composes catalyseurs a metallocene a faible incorporation de comonomere

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JP2817799B2 (ja) * 1989-10-21 1998-10-30 フイナ・テクノロジー・インコーポレーテツド 大粒径の対称的な重合体粒子の製造方法
US5280074A (en) * 1989-12-21 1994-01-18 Hoechst Ag Process for the preparation of a polypropylene molding composition
DE3942365A1 (de) * 1989-12-21 1991-06-27 Hoechst Ag Verfahren zur herstellung einer polypropylen-formmasse
DE3942366A1 (de) * 1989-12-21 1991-06-27 Hoechst Ag Verfahren zur herstellung eines syndiotaktischen propylen-copolymers
DE3942363A1 (de) * 1989-12-21 1991-06-27 Hoechst Ag Verfahren zur herstellung einer polypropylen-formmasse
ATE223440T1 (de) * 1991-03-09 2002-09-15 Basell Polyolefine Gmbh Metallocen und katalysator
DE4139261A1 (de) * 1991-11-29 1993-06-03 Basf Ag Ethylen-copolymerisate niederer dichte
IT1271406B (it) * 1993-09-13 1997-05-28 Spherilene Srl Procedimento per la preparazione di polimeri dell'etilene e prodotti ottenuti
IT1270253B (it) * 1994-06-20 1997-04-29 Spherilene Srl Copolimeri dell'etilene e procedimento per la preparazione di polimeri dell'etilene
UA47394C2 (uk) * 1995-05-16 2002-07-15 Юнівейшн Текнолоджіз, Ллс Етиленовий полімер, який має підвищену придатність до обробки та вирiб, що містить етиленовий полімер
US6225426B1 (en) 1996-04-10 2001-05-01 Uniroyal Chemical Company, Inc. Process for producing polyolefin elastomer employing a metallocene catalyst
US6063536A (en) * 1996-06-04 2000-05-16 Mitsui Petrochemical Industries Ltd. Thermal fixing developer material and wax for electrophotography
JP2002505707A (ja) * 1997-06-14 2002-02-19 ザ ボード オブ トラスティーズ オブ ザ リーランド スタンフォード ジュニア ユニバーシティ エチレン増強高融点熱可塑性エラストマーα−オレフィン重合体合成法（ＰＲＥ／ＥＰＥ効果）
US20060293470A1 (en) * 2005-06-28 2006-12-28 Cao Phuong A Polymerization process using spray-dried catalyst
US8497330B2 (en) * 1997-12-08 2013-07-30 Univation Technologies, Llc Methods for polymerization using spray dried and slurried catalyst
US6242545B1 (en) * 1997-12-08 2001-06-05 Univation Technologies Polymerization catalyst systems comprising substituted hafinocenes
US6479685B2 (en) 1998-01-09 2002-11-12 The Board Of Trustees Of The Leland Standard Junior University Metallocene catalysts for synthesis of high-melting polyolefin copolymer elastomers
AU2111599A (en) 1998-01-09 1999-07-26 Board Of Trustees Of The Leland Stanford Junior University High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis
US6518378B2 (en) 1998-01-09 2003-02-11 The Board Of Trustees Of The Leland Stanford Junior University High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis
US6225427B1 (en) 1998-10-15 2001-05-01 Uniroyal Chemical Company, Inc. Olefin polymerization process employing metallocene catalyst provided by cocatalyst activation of a metallocene procatalyst
KR20010034199A (ko) 1998-11-20 2001-04-25 간디 지오프레이 에이치. 다리화 메탈로센, 제조, 촉매계 내에서의 용도
ATE369909T1 (de) * 2001-06-13 2007-09-15 Beta Technologie Ag Massenpolymerisation-reaktoren und verfahren zur polymerisation
US6936675B2 (en) * 2001-07-19 2005-08-30 Univation Technologies, Llc High tear films from hafnocene catalyzed polyethylenes
BR0211286B1 (pt) * 2001-07-19 2012-10-02 filmes com propriedades fìsicas aperfeiçoadas.
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ES2061877T3 (es) 1994-12-16
DE3836059A1 (de) 1990-05-03
AU4356389A (en) 1990-04-26
ATE99338T1 (de) 1994-01-15
AU615113B2 (en) 1991-09-19
CA1338333C (fr) 1996-05-14
US5086134A (en) 1992-02-04
ZA897954B (en) 1990-07-25
JPH02158611A (ja) 1990-06-19
JP2929544B2 (ja) 1999-08-03
EP0365974B1 (fr) 1993-12-29
DE58906565D1 (de) 1994-02-10
EP0365974A3 (fr) 1992-01-15

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